JP5720772B2 - Exhaust gas purification catalyst, exhaust gas purification monolith catalyst, and method of manufacturing exhaust gas purification catalyst - Google Patents
Exhaust gas purification catalyst, exhaust gas purification monolith catalyst, and method of manufacturing exhaust gas purification catalyst Download PDFInfo
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- JP5720772B2 JP5720772B2 JP2013507669A JP2013507669A JP5720772B2 JP 5720772 B2 JP5720772 B2 JP 5720772B2 JP 2013507669 A JP2013507669 A JP 2013507669A JP 2013507669 A JP2013507669 A JP 2013507669A JP 5720772 B2 JP5720772 B2 JP 5720772B2
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- Prior art keywords
- exhaust gas
- oxide
- gas purification
- carboxylic acid
- purification catalyst
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Description
本発明は、排気ガス浄化触媒、排気ガス浄化モノリス触媒及び排気ガス浄化触媒の製造方法に関する。更に詳細には、本発明は、排気ガス成分の浄化において、優れた性能を発揮し得る排気ガス浄化触媒、排気ガス浄化モノリス触媒及び排気ガス浄化触媒の製造方法に関する。 The present invention relates to an exhaust gas purification catalyst, an exhaust gas purification monolith catalyst, and a method for producing an exhaust gas purification catalyst. More specifically, the present invention relates to an exhaust gas purification catalyst, an exhaust gas purification monolith catalyst, and an exhaust gas purification catalyst manufacturing method capable of exhibiting excellent performance in purification of exhaust gas components.
従来、貴金属を必須成分として用いない浄化触媒について、研究、開発がなされている。そして、排気ガス浄化触媒として、希土類元素と遷移金属元素から構成されるペロブスカイト型の複合酸化物相において、遷移金属元素の一部がジルコニウムなどで置換されたペロブスカイト型複合酸化物を適用したものが提案されている（特許文献１参照。）。
また、低温下で、優れた酸素吸放出性を有し、かつ、この酸素吸放出機能の持続性に優れるＰＭ酸化触媒や排気ガス浄化触媒として、ペロブスカイト型構造を有する複合酸化物であって低温での酸素吸放出性に優れる酸素低温吸放出材と、ペロブスカイト型構造を有する複合酸化物であって酸素移動性に優れる酸素易移動材とを含有するものが提案されている（特許文献２参照。）。Conventionally, research and development have been conducted on purification catalysts that do not use precious metals as essential components. As an exhaust gas purification catalyst, a perovskite complex oxide in which a part of the transition metal element is substituted with zirconium or the like in a perovskite complex oxide phase composed of a rare earth element and a transition metal element is applied. It has been proposed (see Patent Document 1).
Further, it is a complex oxide having a perovskite structure as a PM oxidation catalyst or an exhaust gas purification catalyst having excellent oxygen absorption / release properties at low temperatures and excellent durability of this oxygen absorption / release function. Proposed is a low-temperature oxygen storage / release material having excellent oxygen storage / release properties and a complex oxide having a perovskite structure and an oxygen-moving material having excellent oxygen mobility (see Patent Document 2). .)
しかしながら、上記特許文献１や特許文献２に記載された排気ガス浄化触媒であっても、優れた浄化性能が得られていないという問題点があった。
However, even with the exhaust gas purification catalysts described in
本発明は、このような従来技術の有する課題に鑑みてなされたものである。そして、その目的とするところは、貴金属を必須成分として用いない場合であっても、優れた浄化性能を示す排気ガス浄化触媒、排気ガス浄化モノリス触媒及び排気ガス浄化触媒の製造方法を提供することにある。 The present invention has been made in view of such problems of the prior art. The object is to provide an exhaust gas purification catalyst, an exhaust gas purification monolith catalyst and a method for producing an exhaust gas purification catalyst that exhibit excellent purification performance even when noble metal is not used as an essential component. It is in.
本発明者らは、上記目的を達成するため鋭意検討を重ねた。そして、その結果、貴金属を含まない排気ガス浄化触媒であって、酸素吸放出能を有し、粒子径が１〜５０ｎｍである酸化物であるセリウムとジルコニウムとを含む複合酸化物に、一般式（１）で表され、粒子径が１〜３０ｎｍである酸化物を担持させることにより、上記目的が達成できることを見出し、本発明を完成するに至った。 The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, the exhaust gas purification catalyst does not contain a noble metal, and has a general formula of a complex oxide containing cerium and zirconium, which is an oxide having an oxygen absorption / release capability and a particle diameter of 1 to 50 nm. It has been found that the above object can be achieved by supporting an oxide represented by (1) and having a particle diameter of 1 to 30 nm, and the present invention has been completed.
ＬａｘＭ１−ｘＭ’Ｏ３−δ・・・（１）
（式（１）中、Ｌａはランタン、Ｍはバリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシウム（Ｃａ）からなる群より選ばれる少なくとも１種、Ｍ’は鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）からなる群より選ばれる少なくとも１種、δは酸素欠損量を示し、ｘ及びδは、０＜ｘ≦１、０≦δ≦１の関係を満足する。）La x M 1-x M′O 3-δ (1)
(In the formula (1), La is lanthanum, M is at least one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca), M ′ is iron (Fe), cobalt (Co), (At least one selected from the group consisting of nickel (Ni) and manganese (Mn), δ represents the amount of oxygen deficiency, and x and δ satisfy the
すなわち、本発明の排気ガス浄化触媒は、貴金属を含まない排気ガス浄化触媒であって、酸素吸放出能を有し、粒子径が１〜５０ｎｍである酸化物であるセリウムとジルコニウムとを含む複合酸化物に、一般式（１）で表され、粒子径が１〜３０ｎｍである酸化物が担持されているものである。 That is, the exhaust gas purification catalyst of the present invention is an exhaust gas purification catalyst that does not contain a noble metal, and is a composite containing cerium and zirconium, which is an oxide having an oxygen absorption / release capability and a particle diameter of 1 to 50 nm. An oxide represented by the general formula (1) and having a particle diameter of 1 to 30 nm is supported on the oxide.
ＬａｘＭ１−ｘＭ’Ｏ３−δ・・・（１）
（式（１）中、Ｌａはランタン、Ｍはバリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシウム（Ｃａ）からなる群より選ばれる少なくとも１種、Ｍ’は鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）からなる群より選ばれる少なくとも１種、δは酸素欠損量を示し、ｘ及びδは、０＜ｘ≦１、０≦δ≦１の関係を満足する。）La x M 1-x M′O 3-δ (1)
(In the formula (1), La is lanthanum, M is at least one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca), M ′ is iron (Fe), cobalt (Co), (At least one selected from the group consisting of nickel (Ni) and manganese (Mn), δ represents the amount of oxygen deficiency, and x and δ satisfy the
また、本発明の排気ガス浄化モノリス触媒は、上記本発明の排気ガス浄化触媒を含有する触媒層が、モノリス担体の排気流路に形成されているものである。 The exhaust gas purification monolith catalyst of the present invention is such that a catalyst layer containing the exhaust gas purification catalyst of the present invention is formed in the exhaust flow path of the monolith carrier.
更に、本発明の排気ガス浄化触媒の製造方法は、上記本発明の排気ガス浄化触媒を製造するに当たり、カルボン酸のランタン塩と、カルボン酸のバリウム塩、カルボン酸のストロンチウム塩、カルボン酸のカルシウム塩、カルボン酸の鉄塩、カルボン酸のコバルト塩、カルボン酸のニッケル塩及びカルボン酸のマンガン塩からなる群より選ばれる少なくとも１種のカルボン酸の金属塩とを含む溶液に、酸素吸放出能を有する酸化物を浸漬し、溶液周囲の雰囲気を大気圧より低い減圧状態として、酸素吸放出能を有する酸化物にカルボン酸のランタン塩とカルボン酸の金属塩とを含浸担持させる製造方法である。 Furthermore, the method for producing the exhaust gas purification catalyst of the present invention comprises producing a lanthanum salt of a carboxylic acid, a barium salt of a carboxylic acid, a strontium salt of a carboxylic acid, and a calcium of a carboxylic acid. And a solution containing at least one metal salt of a carboxylic acid selected from the group consisting of a salt, an iron salt of a carboxylic acid, a cobalt salt of a carboxylic acid, a nickel salt of a carboxylic acid, and a manganese salt of a carboxylic acid. Is produced by immersing and supporting an oxide having oxygen in an oxygen absorbing / releasing ability by impregnating and supporting a lanthanum salt of carboxylic acid and a metal salt of carboxylic acid. .
本発明によれば、貴金属を含まない排気ガス浄化触媒であって、酸素吸放出能を有し、粒子径が１〜５０ｎｍである酸化物であるセリウムとジルコニウムとを含む複合酸化物に、一般式（１）で表され、粒子径が１〜３０ｎｍである酸化物を担持させた。 According to the present invention, an exhaust gas purification catalyst that does not contain a noble metal, and has a capability of absorbing and releasing oxygen , and a composite oxide containing cerium and zirconium, which is an oxide having a particle diameter of 1 to 50 nm, An oxide represented by the formula (1) and having a particle size of 1 to 30 nm was supported.
ＬａｘＭ１−ｘＭ’Ｏ３−δ・・・（１）
（式（１）中、Ｌａはランタン、Ｍはバリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシウム（Ｃａ）からなる群より選ばれる少なくとも１種、Ｍ’は鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）からなる群より選ばれる少なくとも１種、δは酸素欠損量を示し、ｘ及びδは、０＜ｘ≦１、０≦δ≦１の関係を満足する。）La x M 1-x M′O 3-δ (1)
(In the formula (1), La is lanthanum, M is at least one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca), M ′ is iron (Fe), cobalt (Co), (At least one selected from the group consisting of nickel (Ni) and manganese (Mn), δ represents the amount of oxygen deficiency, and x and δ satisfy the
そのため、貴金属を必須成分として用いない場合であっても、優れた浄化性能を示す排気ガス浄化触媒、排気ガス浄化モノリス触媒及び排気ガス浄化触媒の製造方法を提供することができる。 Therefore, it is possible to provide a method for producing an exhaust gas purification catalyst, an exhaust gas purification monolith catalyst, and an exhaust gas purification catalyst that exhibit excellent purification performance even when noble metal is not used as an essential component.
以下、本発明の排気ガス浄化触媒、排気ガス浄化モノリス触媒及び排気ガス浄化触媒の製造方法について詳細に説明する。 Hereinafter, the exhaust gas purification catalyst, the exhaust gas purification monolith catalyst, and the method for producing the exhaust gas purification catalyst of the present invention will be described in detail.
［第１の実施形態］
まず、本発明の一実施形態に係る排気ガス浄化触媒について図面を参照しながら詳細に説明する。図１は、第１の実施形態に係る排気ガス浄化触媒を模式的に示す構成図である。同図に示すように、第１の実施形態の排気ガス浄化触媒１は、酸素吸放出能を有する酸化物２に下記一般式（１）で表される酸化物４ａが担持されているものである。また、酸化物４ａの粒子径は代表的には３〜１０ｎｍであ。なお、図１中に参考のために示した一般式（１）で表される酸化物４ｂは、酸素吸放出能を有する酸化物２に担持されているものではない。また、酸化物４ｂの粒子径は代表的には５０ｎｍ超である。[First Embodiment]
First, an exhaust gas purification catalyst according to an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a configuration diagram schematically showing an exhaust gas purification catalyst according to the first embodiment. As shown in the figure, the exhaust
ＬａｘＭ１−ｘＭ’Ｏ３−δ・・・（１）
（式（１）中、Ｌａはランタン、Ｍはバリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシウム（Ｃａ）からなる群より選ばれる少なくとも１種、Ｍ’は鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）からなる群より選ばれる少なくとも１種、δは酸素欠損量を示し、ｘ及びδは、０＜ｘ≦１、０≦δ≦１の関係を満足する。）La x M 1-x M′O 3-δ (1)
(In the formula (1), La is lanthanum, M is at least one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca), M ′ is iron (Fe), cobalt (Co), (At least one selected from the group consisting of nickel (Ni) and manganese (Mn), δ represents the amount of oxygen deficiency, and x and δ satisfy the
ここで、本発明における「酸素吸放出能を有する酸化物に、一般式（１）で表される酸化物が担持されている。」の意味について、「酸化物Ａに酸化物Ｂが担持されている。」という例を用いて詳細に説明する。 Here, the meaning of “an oxide represented by the general formula (1) is supported on the oxide having oxygen absorption / release ability” in the present invention is “an oxide B is supported on the oxide A”. This will be described in detail with reference to an example.
透過型電子顕微鏡（ＴＥＭ）により観察した場合に、酸化物Ａと区別し得る、凝集した状態の酸化物Ｂは、酸化物Ａに担持されているものに該当しない。一方、透過型電子顕微鏡（ＴＥＭ）により観察した場合に、凝集した状態の酸化物Ｂとして酸化物Ａとは区別し得ない酸化物Ｂであって、酸化物Ａをエネルギー分散型Ｘ線分析（ＥＤＸ（測定範囲：ビーム直径５ｎｍ））により元素分析した場合に、酸化物Ａの構成元素と共に酸化物Ｂの構成元素が検出される酸化物Ｂは、酸化物Ａに担持されているものに該当する。もちろん、更に拡大した透過型電子顕微鏡（ＴＥＭ）による観察とＸ線光電子分光（ＸＰＳ）分析により酸化物Ｂを観察できることは言うまでもない。
The aggregated oxide B, which can be distinguished from the oxide A when observed with a transmission electron microscope (TEM), does not correspond to the oxide A supported on the oxide A. On the other hand, when observed with a transmission electron microscope (TEM), the oxide B is an aggregated oxide B that cannot be distinguished from the oxide A, and the oxide A is subjected to energy dispersive X-ray analysis ( When elemental analysis is performed by EDX (measurement range:
このような構成とすることにより、貴金属を必須成分として用いない場合であっても、優れた浄化性能を示す排気ガス浄化触媒となる。 By adopting such a configuration, even if no precious metal is used as an essential component, an exhaust gas purification catalyst that exhibits excellent purification performance is obtained.
現時点においては、下記のような反応メカニズムによってその作用効果が得られていると考えている。しかしながら、このような反応メカニズムによらないでその作用効果が得られている場合であっても、本発明の範囲に含まれることは言うまでもない。 At present, it is considered that the effect is obtained by the following reaction mechanism. However, it goes without saying that even if the action and effect are obtained without relying on such a reaction mechanism, they are included in the scope of the present invention.
図２は、推定される反応メカニズムを説明する図である。同図に示すように、排気ガス浄化触媒１において、酸素吸放出能を有する酸化物２に担持されている一般式（１）で表される酸化物４ａは、触媒反応の活性点として機能する。その際、この酸化物４ａを担持する酸素吸放出能を有する酸化物２は、触媒反応に必要な酸素の吸放出を行うことにより、触媒反応を促進する。これにより、酸素吸放出能が向上し、低温での浄化活性が優れることになる。
FIG. 2 is a diagram for explaining an estimated reaction mechanism. As shown in the figure, in the exhaust
一方、図３は、従来の排気ガス浄化触媒を模式的に示す構成図である。同図に示すように、従来の排気ガス浄化触媒１０は、酸素吸放出能を有する酸化物２に下記一般式（１）で表される酸化物４ｂが、担持されておらず、凝集した状態で存在しているものである。なお、酸化物４ｂは粒子が凝集しており、その凝集体としての粒子径は代表的には１００〜５００ｎｍである。このような構成であると、上記のような反応メカニズムが起こりにくいため、本発明における所望の作用効果が得られないと考えられる。
On the other hand, FIG. 3 is a block diagram schematically showing a conventional exhaust gas purification catalyst. As shown in the figure, in the conventional exhaust
また、第１の実施形態の排気ガス浄化触媒においては、酸素吸放出能を有する酸化物の粒子径が１〜５０ｎｍであることが好ましく、５〜２０ｎｍであることがより好ましい。粒子径が１ｎｍ未満である場合は、酸素吸放出能を有する酸化物が凝集して所望の作用効果が得られない可能性があり、粒子径が５０ｎｍ超の場合には、一般式（１）で表される酸化物が担持されずに所望の作用効果が得られない可能性がある。 Moreover, in the exhaust gas purification catalyst of 1st Embodiment, it is preferable that the particle diameter of the oxide which has oxygen absorption-and-release capability is 1-50 nm, and it is more preferable that it is 5-20 nm. When the particle size is less than 1 nm, the oxide having oxygen absorption / release ability may be aggregated and a desired effect may not be obtained. When the particle size is more than 50 nm, the general formula (1) There is a possibility that a desired effect cannot be obtained without the oxide represented by
そして、第１の実施形態の排気ガス浄化触媒においては、酸素吸放出能を有する酸化物に担持される一般式（１）で表される酸化物の粒子径が１〜３０ｎｍであることが好ましく、３〜１０ｎｍであることが好ましい。粒子径が１ｎｍ未満である場合は、酸素吸放出能を有する酸化物が凝集して所望の作用効果が得られない可能性があり、粒子径が３０ｎｍ超の場合には、一般式（１）で表される酸化物に担持されずに所望の作用効果が得られない可能性がある。特に、粒子径が１０ｎｍ以下の場合には、より優れた浄化性能を示すという観点から好ましい。 In the exhaust gas purification catalyst of the first embodiment, it is preferable that the particle diameter of the oxide represented by the general formula (1) supported by the oxide having oxygen absorption / release capacity is 1 to 30 nm. It is preferable that it is 3-10 nm. When the particle diameter is less than 1 nm, the oxide having oxygen absorption / release ability may aggregate and a desired effect may not be obtained. When the particle diameter exceeds 30 nm, the general formula (1) There is a possibility that a desired effect cannot be obtained without being supported by the oxide represented by In particular, when the particle diameter is 10 nm or less, it is preferable from the viewpoint of showing more excellent purification performance.
また、上述したように、一般式（１）で表される酸化物は、触媒反応の活性点として機能すると考えており、使用量が同じ場合により活性点を多くすることができるという観点から、一般式（１）で表される酸化物の粒子径は、酸素吸放出能を有する酸化物の粒子径より小さいことが好ましい。 Further, as described above, the oxide represented by the general formula (1) is considered to function as an active site of the catalytic reaction, and from the viewpoint that the active site can be increased when the amount used is the same. The particle size of the oxide represented by the general formula (1) is preferably smaller than the particle size of the oxide having oxygen absorption / release capability.
なお、本明細中において、「粒子径」とは、走査型電子顕微鏡（ＳＥＭ）や透過型電子顕微鏡（ＴＥＭ）などの観察手段を用いて観察される酸化物粒子（観察面）の輪郭線上の任意の２点間の距離のうち、最大の距離を意味する。ただし、このような範囲に何ら制限されるものではなく、本発明の作用効果を有効に発現できるものであれば、この範囲を外れていてもよいことは言うまでもない。 In the present specification, the “particle diameter” refers to the contour line of oxide particles (observation surface) observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It means the maximum distance among any two points. However, it is not limited to such a range, and it goes without saying that it may be outside this range as long as the effects of the present invention can be effectively expressed.
更に、第１の実施形態の排気ガス浄化触媒における酸素吸放出能を有する酸化物は、セリウム（Ｃｅ）及びジルコニウム（Ｚｒ）の少なくとも１種を含む酸化物であることが好ましく、セリウム（Ｃｅ）とジルコニウム（Ｚｒ）とを含む複合酸化物であることがより好ましい。セリウム（Ｃｅ）を含む酸化物は酸素吸放出能が酸素吸放出量が多いという観点から優れており、ジルコニウム（Ｚｒ）を含む酸化物は、酸素級放出能が酸素吸放出速度が速いという観点から優れている。そして、セリウム（Ｃｅ）とジルコニウム（Ｚｒ）とを含む複合酸化物は酸素放出量が多く、酸素吸放出速度が速いというの双方の観点から優れている。 Further, the oxide having oxygen absorption / release capability in the exhaust gas purification catalyst of the first embodiment is preferably an oxide containing at least one of cerium (Ce) and zirconium (Zr), and cerium (Ce). More preferably, it is a composite oxide containing zirconium and zirconium (Zr). Oxide containing cerium (Ce) is superior in terms of oxygen absorption / release capacity and a large amount of oxygen absorption / release, and oxides containing zirconium (Zr) have an oxygen class release capacity and a high oxygen absorption / release rate. Is excellent from. A composite oxide containing cerium (Ce) and zirconium (Zr) is excellent from both viewpoints of a large oxygen release amount and a high oxygen absorption / release rate.
なお、セリウムやジルコニウムを含む酸化物としては、例えば、ジルコニウムとセリウムとランタンとネオジムとを含む複合酸化物（Ｚｒ−Ｃｅ−Ｌａ−Ｎｄ−Ｏｘ）やジルコニウムとセリウムとネオジムとを含む複合酸化物（Ｚｒ−Ｃｅ−Ｎｄ−Ｏｘ）、ジルコニウムとランタンとを含む（Ｚｒ−Ｌａ−Ｏｘ）などを挙げることができるが、これらに限定されるものではない。すなわち、酸素吸放出能を有するものであれば、従来公知の材料を適用することができる。例えば、セリウムとジルコニウムを含有する酸化物であって、セリウムやジルコニウムの一部がアルカリ金属元素やアルカリ土類金属元素、希土類元素などで置換されたものを挙げることができる。 As the oxide containing cerium or zirconium, for example, a composite oxide containing zirconium, cerium, lanthanum, and neodymium (Zr—Ce—La—Nd—Ox) or a composite oxide containing zirconium, cerium, and neodymium is used. (Zr—Ce—Nd—Ox), (Zr—La—Ox) containing zirconium and lanthanum can be exemplified, but not limited thereto. That is, a conventionally known material can be applied as long as it has oxygen absorption / release capability. For example, an oxide containing cerium and zirconium, in which part of cerium or zirconium is substituted with an alkali metal element, an alkaline earth metal element, a rare earth element, or the like can be given.
また、第１の実施形態の排気ガス浄化触媒における酸素吸放出能を有する酸化物が、セリウム（Ｃｅ）とジルコニウム（Ｚｒ）とを含む複合酸化物である場合には、複合酸化物中のセリウム含有量がセリウム酸化物（ＣｅＯ２）換算で５質量％以上であることがＣＯ転化率が向上するという観点から好ましく、２０質量％以上であることＣＯ転化率がより向上するという観点からより好ましい。より具体的には、複合酸化物中のセリウム含有量がセリウム酸化物（ＣｅＯ２）換算で５質量％以上９０質量％以下であることが好ましく、２０質量％以上８０質量％以下であることがより好ましい。複合酸化物中のセリウム含有量がセリウム酸化物（ＣｅＯ２）換算で９０質量％超とするとＣＯ転化率の向上効果が低下するおそれがある。Further, when the oxide having oxygen absorption / release capability in the exhaust gas purification catalyst of the first embodiment is a composite oxide containing cerium (Ce) and zirconium (Zr), cerium in the composite oxide The content is preferably 5% by mass or more in terms of cerium oxide (CeO 2 ) from the viewpoint of improving the CO conversion rate, and more preferably 20% by mass or more from the viewpoint of further improving the CO conversion rate. . More specifically, the cerium content in the composite oxide is preferably 5% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less in terms of cerium oxide (CeO 2 ). More preferred. If the cerium content in the composite oxide exceeds 90% by mass in terms of cerium oxide (CeO 2 ), the effect of improving the CO conversion rate may be reduced.
更に、第１の実施形態の排ガス浄化触媒における一般式（１）で表される酸化物は、ペロブスカイト型酸化物であることが好ましい。ペロブスカイト型酸化物であると、結晶構造を有しているため耐久性が優れたものとなる利点がある。 Furthermore, the oxide represented by the general formula (1) in the exhaust gas purification catalyst of the first embodiment is preferably a perovskite oxide. A perovskite oxide has an advantage that it has excellent durability because it has a crystal structure.
［第２の実施形態］
次に、本発明の一実施形態に係る排気ガス浄化触媒の製造方法について、上述した本発明の一実施形態に係る排気ガス浄化触媒を挙げて詳細に説明する。但し、本発明の排気ガス浄化触媒は、このような製造方法により作製されたものに限定されるものではない。[Second Embodiment]
Next, a method for manufacturing an exhaust gas purification catalyst according to an embodiment of the present invention will be described in detail with reference to the above-described exhaust gas purification catalyst according to an embodiment of the present invention. However, the exhaust gas purification catalyst of the present invention is not limited to the one produced by such a production method.
第１の実施形態の排気ガス浄化触媒は、例えば以下のような製造方法により作製することができる。 The exhaust gas purification catalyst of the first embodiment can be produced, for example, by the following production method.
まず、酸素吸放出能を有する酸化物として、セリウムとジルコニウムとを含む蛍石型酸化物粒子の凝集体を用意する。 First, an aggregate of fluorite-type oxide particles containing cerium and zirconium is prepared as an oxide having oxygen absorption / release capability.
また、一般式（１）で表される酸化物における組成が所望のものとなるように調製した、カルボン酸のランタン塩と、カルボン酸のバリウム塩、カルボン酸のストロンチウム塩、カルボン酸のカルシウム塩、カルボン酸の鉄塩、カルボン酸のコバルト塩、カルボン酸のニッケル塩及びカルボン酸のマンガン塩からなる群より選ばれる少なくとも１種のカルボン酸の金属塩とを含む溶液を用意する。 In addition, a lanthanum salt of a carboxylic acid, a barium salt of a carboxylic acid, a strontium salt of a carboxylic acid, and a calcium salt of a carboxylic acid, prepared so that the composition of the oxide represented by the general formula (1) is as desired. And a solution containing at least one metal salt of carboxylic acid selected from the group consisting of iron salt of carboxylic acid, cobalt salt of carboxylic acid, nickel salt of carboxylic acid and manganese salt of carboxylic acid.
次いで、得られた溶液に、得られた酸素吸放出能を有する酸化物を浸漬する。この際、溶液周囲の雰囲気をアスピレータなどを用いて大気圧より低い減圧状態として、酸素吸放出能を有する酸化物の細孔中の気体を脱気して、溶液が含浸担持され易くする。 Next, the obtained oxide having oxygen absorbing / releasing ability is immersed in the obtained solution. At this time, the atmosphere around the solution is reduced to a pressure lower than the atmospheric pressure using an aspirator or the like, and the gas in the pores of the oxide having oxygen absorption / release capability is degassed to facilitate the impregnation of the solution.
しかる後、カルボン酸のランタン塩とカルボン酸の金属塩とが含浸担持された酸素吸放出能を有する酸化物を、乾燥、４００℃程度で仮焼成、７００℃程度で本焼成することにより、第１の実施形態の排気ガス浄化触媒を得ることができる。 Thereafter, the oxide having oxygen absorption / release ability impregnated and supported with a lanthanum salt of carboxylic acid and a metal salt of carboxylic acid is dried, pre-baked at about 400 ° C., and finally fired at about 700 ° C. The exhaust gas purification catalyst of one embodiment can be obtained.
例えば、硝酸のランタン塩及び硝酸の金属塩のみを用いた場合には、粘性が殆どないため細孔中に含浸されやすい一方、乾燥や焼成に際して、溶液の蒸発とともに移動し易く、担持されにくい。一方、カルボン酸のランタン塩やカルボン酸の金属塩を用いた場合には、これらは金属錯体塩を形成し、粘性があるため、細孔中の気体を脱気することにより、細孔中に含浸させることができる。一方、乾燥や焼成に際してはこれらの金属錯体塩は粘性があるため、溶液の蒸発とともに移動し難く、担持されることとなる。 For example, when only a lanthanum nitrate salt and a metal salt of nitric acid are used, since there is almost no viscosity, the pores are easily impregnated. On the other hand, during drying and firing, they easily move with evaporation of the solution and are not easily supported. On the other hand, when a lanthanum salt of carboxylic acid or a metal salt of carboxylic acid is used, these form a metal complex salt and are viscous, so by degassing the gas in the pores, Can be impregnated. On the other hand, since these metal complex salts are viscous during drying and firing, they are difficult to move with the evaporation of the solution and are supported.
なお、カルボン酸としては、１〜４個のカルボキシル基を有するものを挙げることができる。例えばグルコン酸、リンゴ酸、マレイン酸、酢酸、コハク酸、フマル酸、プロピオン酸、メタクリル酸、アクリル酸、クエン酸、酒石酸、イタコン酸、蟻酸、酢酸、マロン酸などを挙げることができる。その中でも、乳酸を用いることが好ましい。 Examples of the carboxylic acid include those having 1 to 4 carboxyl groups. Examples thereof include gluconic acid, malic acid, maleic acid, acetic acid, succinic acid, fumaric acid, propionic acid, methacrylic acid, acrylic acid, citric acid, tartaric acid, itaconic acid, formic acid, acetic acid and malonic acid. Of these, lactic acid is preferably used.
［第３の実施形態］
次に、本発明の一実施形態に係る排気ガス浄化モノリス触媒について図面を参照しながら詳細に説明する。図４は、第３の実施形態に係る排気ガス浄化モノリス触媒を模式的に示す構成図である。同図に示すように、第３の実施形態の排気ガス浄化モノリス触媒１０は、上述した第１の実施形態の排気ガス浄化触媒を含有する触媒層１２が、モノリス担体１４の排気流路１４ａに形成されているものである。なお、モノリス担体としては、コーディエライトなどのセラミックスやフェライト系ステンレスなどの金属等の耐熱性材料から成るものなどを挙げることができる。[Third Embodiment]
Next, an exhaust gas purification monolith catalyst according to an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 4 is a configuration diagram schematically illustrating an exhaust gas purification monolith catalyst according to a third embodiment. As shown in the figure, in the exhaust gas
このような構成とすることにより、貴金属を必須成分として用いない場合であっても、優れた浄化性能を示す排気ガス浄化触媒となる。特に、排気ガスの流速が速い場合にも優れた浄化性能を示すことができる。 By adopting such a configuration, even if no precious metal is used as an essential component, an exhaust gas purification catalyst that exhibits excellent purification performance is obtained. In particular, excellent purification performance can be exhibited even when the exhaust gas flow rate is high.
以下、本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
（実施例１）
ランタンを含む乳酸溶液と鉄を含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７２質量％ＺｒＯ２−２１質量％ＣｅＯ２−５質量％Ｎｄ２Ｏ３−２質量％Ｌａ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、ＬａＦｅＯ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＦｅＯ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。Example 1
A lactic acid solution containing lanthanum and a lactic acid solution containing iron were impregnated in a Ce-Zr-based oxide (72 mass% ZrO 2 -21 mass% CeO 2 -5 mass% Nd 2 O 3 -2 mass% La 2 O 3 ). Then, the pressure was reduced for 1 hour, and then calcined in the air at 400 ° C. for 2 hours and at 700 ° C. for 5 hours to obtain the exhaust gas purification catalyst of this example. Note that the mass ratio of LaFeO 3 and Ce—Zr-based oxide is LaFeO 3 : Ce—Zr-based oxide = 30: 70. The particle size was measured by observation with a scanning electron microscope (SEM). Table 1 shows a part of the specification of the exhaust gas purification catalyst of this example.
図５は、本例の排気ガス浄化触媒の透過型電子顕微鏡（ＴＥＭ）写真である。また、図６は、図５に示す領域Ａにおけるエネルギー分散型Ｘ線分析の結果である。更に、図７は、図５に示す領域Ｂにおけるエネルギー分散型Ｘ線分析の結果である。更にまた、図８は、図５に示す領域Ａにおける透過型電子顕微鏡写真である。 FIG. 5 is a transmission electron microscope (TEM) photograph of the exhaust gas purification catalyst of this example. FIG. 6 shows the result of energy dispersive X-ray analysis in region A shown in FIG. Further, FIG. 7 shows the result of energy dispersive X-ray analysis in the region B shown in FIG. FIG. 8 is a transmission electron micrograph in the region A shown in FIG.
図６に示すように、領域Ａに観察される約１０ｎｍの粒子からは、エネルギー分散型Ｘ線分析（ＥＤＸ）による元素分析により主に、ジルコニウム（Ｚｒ）、セリウム（Ｃｅ）が検出され、更にランタン（Ｌａ）、ネオジム（Ｎｄ）及び鉄（Ｆｅ）が検出された。一方、図７に示すように、領域Ｂに観察される約５０ｎｍ超の粒子からは、主に鉄（Ｆｅ）とランタン（Ｌａ）が検出された。更に、蛍石型酸化物であるＣｅ−Ｚｒ系酸化物粒子とペロブスカイト型酸化物であるＬａＦｅＯ３粒子が存在していることが、図８における干渉縞の周期と別途測定したＸ線光電子分光（ＸＰＳ）分析とから分かった。なお、各実施例においても、同様の測定結果が得られた。As shown in FIG. 6, zirconium (Zr) and cerium (Ce) are mainly detected from the particle of about 10 nm observed in the region A by elemental analysis by energy dispersive X-ray analysis (EDX). Lanthanum (La), neodymium (Nd) and iron (Fe) were detected. On the other hand, as shown in FIG. 7, iron (Fe) and lanthanum (La) were mainly detected from the particles of about 50 nm observed in the region B. Furthermore, the presence of Ce—Zr-based oxide particles that are fluorite-type oxides and LaFeO 3 particles that are perovskite-type oxides indicate the period of interference fringes in FIG. XPS analysis. In each example, similar measurement results were obtained.
（実施例２）
ランタンを含む乳酸溶液とニッケルを含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７２質量％ＺｒＯ２−２１質量％ＣｅＯ２−５質量％Ｎｄ２Ｏ３−２質量％Ｌａ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、ＬａＮｉＯ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＮｉＯ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。(Example 2)
A lactic acid solution containing lanthanum and a lactic acid solution containing nickel were impregnated in a Ce-Zr-based oxide (72 mass% ZrO 2 -21 mass% CeO 2 -5 mass% Nd 2 O 3 -2 mass% La 2 O 3 ). Then, the pressure was reduced for 1 hour, and then calcined in the air at 400 ° C. for 2 hours and at 700 ° C. for 5 hours to obtain the exhaust gas purification catalyst of this example. Note that the mass ratio of LaNiO 3 and Ce—Zr-based oxide is LaNiO 3 : Ce—Zr-based oxide = 30: 70. The particle size was measured by observation with a scanning electron microscope (SEM). Table 1 shows a part of the specification of the exhaust gas purification catalyst of this example.
（実施例３）
ランタンを含む乳酸溶液とマンガンを含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７２質量％ＺｒＯ２−２１質量％ＣｅＯ２−５質量％Ｎｄ２Ｏ３−２質量％Ｌａ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、ＬａＭｎＯ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＭｎＯ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。(Example 3)
A lactic acid solution containing lanthanum and a lactic acid solution containing manganese were impregnated in a Ce-Zr-based oxide (72% by mass ZrO 2 -21% by mass CeO 2 -5% by mass Nd 2 O 3 -2% by mass La 2 O 3 ). Then, the pressure was reduced for 1 hour, and then calcined in the air at 400 ° C. for 2 hours and at 700 ° C. for 5 hours to obtain the exhaust gas purification catalyst of this example. Note that the mass ratio of LaMnO 3 and Ce—Zr-based oxide is LaMnO 3 : Ce—Zr-based oxide = 30: 70. The particle size was measured by observation with a scanning electron microscope (SEM). Table 1 shows a part of the specification of the exhaust gas purification catalyst of this example.
（実施例４）
ランタンを含む乳酸溶液とストロンチウムを含む乳酸溶液と鉄を含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７０質量％ＺｒＯ２−２０質量％ＣｅＯ２−１０質量％Ｎｄ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、Ｌａ０．８Ｓｒ０．２ＦｅＯ３とＣｅ−Ｚｒ系酸化物の質量比は、Ｌａ０．８Ｓｒ０．２ＦｅＯ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。Example 4
Lanthanum was impregnated with lactic acid solution Ce-Zr-based oxide (70 wt% ZrO 2 -20 wt% CeO 2 -10
（実施例５）
ランタンを含む乳酸溶液と鉄を含む乳酸溶液とマンガンを含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７０質量％ＺｒＯ２−２０質量％ＣｅＯ２−１０質量％Ｎｄ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、ＬａＦｅ０．８Ｍｎ０．２Ｏ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＦｅ０．８Ｍｎ０．２Ｏ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。(Example 5)
Lanthanum was impregnated with lactic acid solution containing lactic acid solution and manganese containing lactic acid solution and iron Ce-Zr-based oxide (70 wt% ZrO 2 -20 wt% CeO 2 -10
（実施例６）
ランタンを含む乳酸溶液と鉄を含む乳酸溶液とニッケルを含む乳酸溶液をＣｅ−Ｚｒ系酸化物（７０質量％ＺｒＯ２−２０質量％ＣｅＯ２−１０質量％Ｎｄ２Ｏ３）に含浸し、次いで、１時間減圧させ、しかる後、４００℃で２時間、７００℃で５時間、空気中で焼成して、本例の排気ガス浄化触媒を得た。なお、ＬａＦｅ０．８Ｎｉ０．２Ｏ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＦｅ０．８Ｎｉ０．２Ｏ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。本例の排気ガス浄化触媒の仕様の一部を表１に示す。(Example 6)
Lanthanum was impregnated with lactic acid solution Ce-Zr-based oxide (70 wt% ZrO 2 -20 wt% CeO 2 -10
（比較例１）
ランタンを含む硝酸溶液と鉄を含む硝酸溶液をＣｅ−Ｚｒ系酸化物（７２質量％ＺｒＯ２−２１質量％ＣｅＯ２−５質量％Ｎｄ２Ｏ３−２質量％Ｌａ２Ｏ３）に含浸し、次いで、１５０℃で一晩乾燥させ、更に乳鉢で粉砕し、しかる後、４００℃で2時間、７００℃で５時間、空気中で焼成して、本例の酸化物を得た。なお、ＬａＦｅＯ３とＣｅ−Ｚｒ系酸化物の質量比は、ＬａＦｅＯ３：Ｃｅ−Ｚｒ系酸化物＝３０：７０である。また、粒子径は、走査型電子顕微鏡（ＳＥＭ）による観察によって測定した。ＬａＦｅＯ３粒子の凝集体の粒子径は、１００〜５００ｎｍであった。本例の排気ガス浄化触媒の仕様の一部を表１に示す。(Comparative Example 1)
A nitric acid solution containing lanthanum and a nitric acid solution containing iron were impregnated in a Ce-Zr-based oxide (72 mass% ZrO 2 -21 mass% CeO 2 -5 mass% Nd 2 O 3 -2 mass% La 2 O 3 ). Then, it was dried at 150 ° C. overnight, further pulverized in a mortar, and then calcined in air at 400 ° C. for 2 hours and 700 ° C. for 5 hours to obtain the oxide of this example. Note that the mass ratio of LaFeO 3 and Ce—Zr-based oxide is LaFeO 3 : Ce—Zr-based oxide = 30: 70. The particle size was measured by observation with a scanning electron microscope (SEM). The particle diameter of the aggregate of LaFeO 3 particles was 100 to 500 nm. Table 1 shows a part of the specification of the exhaust gas purification catalyst of this example.
図９は、本例の排気ガス浄化触媒の透過型電子顕微鏡（ＴＥＭ）写真である。また、図１０は、図９に示す領域Ａにおけるエネルギー分散型Ｘ線分析の結果である。更に、図１１は、図９に示す領域Ｂにおけるエネルギー分散型Ｘ線分析の結果である。 FIG. 9 is a transmission electron microscope (TEM) photograph of the exhaust gas purification catalyst of this example. FIG. 10 shows the results of energy dispersive X-ray analysis in region A shown in FIG. Further, FIG. 11 shows the result of the energy dispersive X-ray analysis in the region B shown in FIG.
図１０に示すように、領域Ａに観察される凝集体からは、エネルギー分散型Ｘ線分析（ＥＤＸ）による元素分析により、主に、鉄（Ｆｅ）とランタン（Ｌａ）が検出された。一方、図１１に示すように、領域Ｂに観察されるマトリックスからは、主に、ジルコニウム（Ｚｒ）とセリウム（Ｃｅ）が検出された。 As shown in FIG. 10, iron (Fe) and lanthanum (La) were mainly detected from the aggregates observed in the region A by elemental analysis by energy dispersive X-ray analysis (EDX). On the other hand, as shown in FIG. 11, mainly from the matrix observed in the region B, zirconium (Zr) and cerium (Ce) were detected.
［性能評価］
各例の排気ガス浄化触媒を用いて浄化性能を評価した。得られた結果を表２に示す。[Performance evaluation]
The purification performance was evaluated using the exhaust gas purification catalyst of each example. The obtained results are shown in Table 2.
＜粉末評価＞
各例の排気ガス浄化触媒に対して、下記条件下、四重極質量分析装置を用いてＣＯ２を測定した。ＣＯ転化率は下記式（Ｉ）より算出した。<Powder evaluation>
For the exhaust gas purification catalyst of each example, CO 2 was measured using a quadrupole mass spectrometer under the following conditions. The CO conversion was calculated from the following formula (I).
（評価条件）
・触媒量：０．２ｇ（粉末）
・流量 ：５０ｃｍ３／ｍｉｎ
・ガス組成：ＣＯ；０．４体積％、Ｏ２；０．２体積％、Ｈｅ；バランス(Evaluation conditions)
-Catalyst amount: 0.2 g (powder)
・ Flow rate: 50 cm 3 / min
Gas composition: CO; 0.4% by volume, O 2 ; 0.2% by volume, He; balance
ＣＯ転化率（％）＝Ａ×（ＣＯ２ｏｕｔ）＋Ｂ・・・（Ｉ）
（予め、ＣＯが１００％反応したときの質量数４４の質量分析計の値をＣＯ２生成率１００％とし、また、ＣＯが０％反応したときの質量数４４の質量分析計の値をＣＯ２生成率０％とし、検量線を作成する。これをＹ＝Ａｘ＋Ｂとし、ｘは質量分析計の質量数４４の値とする。ｘは触媒出口のＣＯ２であり、式（１）で（ＣＯ２ｏｕｔ）と表記する。）CO conversion rate (%) = A × (CO 2out ) + B (I)
(The mass spectrometer value of mass number 44 when 100% of CO reacts in advance is defined as 100% CO 2 production rate, and the mass spectrometer value of mass number 44 when CO reacts 0% is defined as
＜ラボ評価＞
各例の排気ガス浄化触媒とベーマイトアルミナ、硝酸及びイオン交換水とを用いて得られた各例の触媒スラリーを作製し、これを用いて各例の排気ガス浄化モノリス触媒を得た。各例の排気ガス浄化モノリス触媒に対して、下記条件下、排気ガス分析装置（堀場製作所製、ＭＥＸＡ−７１００Ｄ）を用いてＣＯ濃度を測定した。ＣＯ転化率は下記式（ＩＩ）より算出した。<Lab evaluation>
The catalyst slurry of each example obtained using the exhaust gas purification catalyst of each example and boehmite alumina, nitric acid, and ion-exchanged water was produced, and the exhaust gas purification monolith catalyst of each example was obtained using this. For the exhaust gas purifying monolith catalyst of each example, the CO concentration was measured using an exhaust gas analyzer (manufactured by Horiba, Ltd., MEXA-7100D) under the following conditions. The CO conversion was calculated from the following formula (II).
（評価条件）
・触媒容量：１１９ｃｍ３
・ガス流量：４０Ｌ／ｍｉｎ
・ガス組成（ストイキ）：Ｏ２；０．６体積％、ＣＯ；０．６体積％、ＮＯ；１０００体積ｐｐｍ、ＨＣ；１６６５体積ｐｐｍＣ、Ｈ２；０．２体積％、Ｈ２Ｏ；１０体積％、ＣＯ２；１３．９体積％(Evaluation conditions)
Catalyst capacity: 119 cm 3
・ Gas flow rate: 40L / min
Gas composition (stoichiometric): O 2 ; 0.6 vol%, CO; 0.6 vol%, NO; 1000 vol ppm, HC; 1665 vol ppm C, H 2 ; 0.2 vol%, H 2 O; 10 Volume%, CO 2 ; 13.9 volume%
ＣＯ転化率（％）＝（ＣＯｉｎ−ＣＯｏｕｔ）／ＣＯｉｎ×１００・・・（ＩＩ）
（式（ＩＩ）中、ＣＯｉｎは、サンプルを通さない場合のガスに対しての排気ガス分析装置のＣＯ濃度、ＣＯｏｕｔは、サンプル通過後のガスに対しての排気ガス分析装置のＣＯ濃度を示す。）CO conversion rate (%) = (CO in −CO out ) / CO in × 100 (II)
(In Formula (II), CO in is the CO concentration of the exhaust gas analyzer with respect to the gas that does not pass through the sample, and CO out is the CO concentration of the exhaust gas analyzer with respect to the gas after passing through the sample. Is shown.)
＜台上評価＞
各例の排気ガス浄化触媒とベーマイトアルミナ、硝酸及びイオン交換水とを用いて得られた各例の触媒スラリーを作製し、これを用いて各例の排気ガス浄化モノリス触媒を得た。各例の排気ガス浄化モノリス触媒に対して、下記条件下、排気ガス分析装置（堀場製作所製、ＭＥＸＡ−７５００Ｄ）を用いてＣＯ濃度を測定した。ＣＯ転化率は上記式（ＩＩ）より算出した。<Bench evaluation>
The catalyst slurry of each example obtained using the exhaust gas purification catalyst of each example and boehmite alumina, nitric acid, and ion-exchanged water was produced, and the exhaust gas purification monolith catalyst of each example was obtained using this. For the exhaust gas purifying monolith catalyst of each example, the CO concentration was measured using an exhaust gas analyzer (manufactured by Horiba, MEXA-7500D) under the following conditions. The CO conversion was calculated from the above formula (II).
（評価条件）
・日産自動車製エンジン使用
・触媒容量：１１９ｃｍ３
・ガス流量：６０ｍ３／ｈ
・ガス組成（ストイキ）：ＨＣ；約２０００体積ｐｐｍＣ、ＣＯ；約０．５４体積％、ＮＯ；約１５００体積ｐｐｍ、Ｏ２；約０．５６体積％、ＣＯ２；１４．６体積％(Evaluation conditions)
・ Uses Nissan engine ・ Catalyst capacity: 119cm 3
・ Gas flow rate: 60 m 3 / h
Gas composition (stoichi): HC; about 2000 ppm by volume, CO; about 0.54% by volume, NO; about 1500 ppm by volume, O 2 ; about 0.56% by volume, CO 2 ; 14.6% by volume
表１及び表２より、本発明の範囲に属する実施例１〜６は、本発明外の比較例１と比較して、一酸化炭素の転化率が高く、酸化性能が優れていることが分かる。現時点においては、実施例１や実施例４が特に優れていると考えられる。 From Table 1 and Table 2, it can be seen that Examples 1 to 6 belonging to the scope of the present invention have a higher carbon monoxide conversion rate and superior oxidation performance as compared with Comparative Example 1 outside the present invention. . At present, Example 1 and Example 4 are considered to be particularly excellent.
＜台上評価２＞
実施例４において、Ｃｅ−Ｚｒ系酸化物に替えてセリア量をそれぞれ変更したセリアジルコニア複合酸化物と、ベーマイトアルミナ、硝酸及びイオン交換水とを用いて得られた各例の触媒スラリーを作製し、これを用いて各例の排気ガス浄化モノリス触媒を得た。各例の排気ガス浄化モノリス触媒に対して、下記条件下、排気ガス分析装置（堀場製作所製、ＭＥＸＡ−９１００）を用いてＣＯ濃度を測定した。ＣＯ転化率は上記式（ＩＩ）より算出した。得られた結果を図１２に示す。<
In Example 4, the catalyst slurry of each example obtained using ceria zirconia composite oxide in which the amount of ceria was changed in place of the Ce-Zr-based oxide, boehmite alumina, nitric acid and ion-exchanged water was prepared. Using this, the exhaust gas purifying monolith catalyst of each example was obtained. With respect to the exhaust gas purification monolith catalyst of each example, the CO concentration was measured using an exhaust gas analyzer (manufactured by Horiba, Ltd., MEXA-9100) under the following conditions. The CO conversion was calculated from the above formula (II). The obtained result is shown in FIG.
（評価条件）
・日産自動車製エンジン使用
・触媒コート量：２６８ｇ／Ｌ＋ＤＰＲ：３２ｇ／Ｌ
・ガス流量：６０ｍ３／ｈ
・Ａ／Ｆ振幅：±０．２、１．０Ｈｚ
・ガス組成（ストイキ）：ＨＣ；約２０００体積ｐｐｍＣ、ＣＯ；約０．５４体積％、ＮＯ；約１５００体積ｐｐｍ、Ｏ２；約０．５６体積％、ＣＯ２；１４．６体積％(Evaluation conditions)
-Use Nissan engine-Catalyst coating amount: 268g / L + DPR: 32g / L
・ Gas flow rate: 60 m 3 / h
A / F amplitude: ± 0.2, 1.0 Hz
Gas composition (stoichi): HC; about 2000 ppm by volume, CO; about 0.54% by volume, NO; about 1500 ppm by volume, O 2 ; about 0.56% by volume, CO 2 ; 14.6% by volume
図１２より、セリアジルコニア複合酸化物中のセリア（ＣｅＯ２）量は５質量％以上であることが好ましく、２０質量％以上であることが好ましいことが分かる。特に、５〜９０質量％であることが好ましく、２０〜８０質量％であることが好ましいことが分かる。FIG. 12 shows that the amount of ceria (CeO 2 ) in the ceria zirconia composite oxide is preferably 5% by mass or more, and more preferably 20% by mass or more. It turns out that it is especially preferable that it is 5-90 mass%, and it is preferable that it is 20-80 mass%.
１、１００ 排気ガス浄化触媒
２ 酸素吸放出能を有する酸化物
４ａ、４ｂ 一般式（１）で表される酸化物
１０ 排気ガス浄化モノリス触媒
１２ 触媒層
１４ モノリス担体DESCRIPTION OF SYMBOLS 1,100 Exhaust-
Claims (7)
酸素吸放出能を有する酸化物に、一般式（１）
ＬａｘＭ１−ｘＭ’Ｏ３−δ・・・（１）
（式（１）中、Ｌａはランタン、Ｍはバリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシウム（Ｃａ）からなる群より選ばれる少なくとも１種、Ｍ’は鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）及びマンガン（Ｍｎ）からなる群より選ばれる少なくとも１種、δは酸素欠損量を示し、ｘ及びδは、０＜ｘ≦１、０≦δ≦１の関係を満足する。）で表される酸化物が担持されており、
上記酸素吸放出能を有する酸化物の粒子径が、１〜５０ｎｍであり、
上記一般式（１）で表される酸化物の粒子径が、１〜３０ｎｍであり、
上記酸素吸放出能を有する酸化物が、セリウムとジルコニウムとを含む複合酸化物である
ことを特徴とする排気ガス浄化触媒。 An exhaust gas purification catalyst containing no precious metal,
An oxide having oxygen absorbing / releasing ability is represented by the general formula (1)
La x M 1-x M′O 3-δ (1)
(In the formula (1), La is lanthanum, M is at least one selected from the group consisting of barium (Ba), strontium (Sr) and calcium (Ca), M ′ is iron (Fe), cobalt (Co), (At least one selected from the group consisting of nickel (Ni) and manganese (Mn), δ represents the amount of oxygen deficiency, and x and δ satisfy the relationship 0 <x ≦ 1, 0 ≦ δ ≦ 1.) An oxide represented by
The particle size of the oxide having oxygen absorption / release capacity is 1 to 50 nm,
The particle size of the oxide represented by the general formula (1) is Ri 1~30nm der,
The exhaust gas purifying catalyst , wherein the oxide having oxygen absorbing / releasing ability is a composite oxide containing cerium and zirconium .
上記一般式（１）で表される酸化物の粒子径が、３〜１０ｎｍである
ことを特徴とする請求項１に記載の排気ガス浄化触媒。 The particle size of the oxide having oxygen absorption / release capacity is 5 to 20 nm,
The exhaust gas purification catalyst according to claim 1, wherein a particle diameter of the oxide represented by the general formula (1) is 3 to 10 nm.
カルボン酸のランタン塩と、カルボン酸のバリウム塩、カルボン酸のストロンチウム塩、カルボン酸のカルシウム塩、カルボン酸の鉄塩、カルボン酸のコバルト塩、カルボン酸のニッケル塩及びカルボン酸のマンガン塩からなる群より選ばれる少なくとも１種のカルボン酸の金属塩とを含む溶液に、酸素吸放出能を有する酸化物を浸漬し、溶液周囲の雰囲気を大気圧より低い減圧状態として、酸素吸放出能を有する酸化物にカルボン酸のランタン塩とカルボン酸の金属塩とを含浸担持させる、ことを特徴とする排気ガス浄化触媒の製造方法。 In producing the exhaust gas purification catalyst according to any one of claims 1 to 5 ,
Containing lanthanum salt of carboxylic acid, barium salt of carboxylic acid, strontium salt of carboxylic acid, calcium salt of carboxylic acid, iron salt of carboxylic acid, cobalt salt of carboxylic acid, nickel salt of carboxylic acid and manganese salt of carboxylic acid An oxygen absorbing / releasing ability is obtained by immersing an oxide having oxygen absorbing / releasing ability in a solution containing at least one metal salt of a carboxylic acid selected from the group, and setting the atmosphere around the solution at a reduced pressure lower than atmospheric pressure. A method for producing an exhaust gas purification catalyst, wherein an oxide is impregnated with a lanthanum salt of a carboxylic acid and a metal salt of a carboxylic acid.
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Also Published As
| Publication number | Publication date |
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| CN103402630B (en) | 2015-11-25 |
| US9101914B2 (en) | 2015-08-11 |
| US20140018235A1 (en) | 2014-01-16 |
| EP2692432A1 (en) | 2014-02-05 |
| EP2692432B1 (en) | 2019-11-13 |
| JPWO2012133526A1 (en) | 2014-07-28 |
| EP2692432A4 (en) | 2014-10-29 |
| CN103402630A (en) | 2013-11-20 |
| WO2012133526A1 (en) | 2012-10-04 |
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